Propenylamines and methods of making and using same

ABSTRACT

A composition includes a perfluorinated propenylamine represented by the following general formula (1): 
     Each occurrence of R f1  and R f2  is:
         (i) independently a linear or branched perfluoroalkyl group having 1-8 carbon atoms and optionally comprises one or more catenated heteroatoms; or   (ii) bonded together to form a ring structure having 4-8 carbon atoms and that optionally comprises one or more catenated heteroatoms.       

     At least 60 wt. % of the perfluorinated propenylamine is in the form of the E isomer, based on the total weight of the perfluorinated propenylamine in the composition.

FIELD

The present disclosure relates to propenylamines and methods of makingand using the same, and to working fluids that include the same.

BACKGROUND

Various propenylamine compounds are described in, for example, T. Abe,JP 01070444A; T. Abe, JP 0107445A; and M. Bulinski, WO 2015/095285.

SUMMARY

In some embodiments, a composition is provided. The composition includesa perfluorinated propenylamine represented by the following generalformula (1):

Each occurrence of R_(f1) and R_(f2) is:

-   -   (i) independently a linear or branched perfluoroalkyl group        having 1-8 carbon atoms and optionally comprises one or more        catenated heteroatoms; or    -   (ii) bonded together to form a ring structure having 4-8 carbon        atoms and that optionally comprises one or more catenated        heteroatoms; and        At least 60 wt. % of the perfluorinated propenylamine is in the        form of the E isomer, based on the total weight of the        perfluorinated propenylamine in the composition.

In some embodiments, a method of making the above-described compositionis provided. The method includes contacting a perfluorinated allylamineof general formula (2) with an active isomerization catalyst;

and carrying out a selective catalytic isomerization to form a1-propenylamine of general formula (1);

The selectivity for formation of the E isomer of formula (1) is at least60% wt. %, based on the total weight of the propenylamine in thecomposition.

In some embodiments, a working fluid is provided. The working fluidincludes the above-described composition. The above-describedcomposition is present in the working fluid at an amount of at least 25%by weight, based on the total weight of the working fluid.

In some embodiments, an apparatus for heat transfer is provided. Theapparatus includes a device; and a mechanism for transferring heat to orfrom the device. The mechanism includes a heat transfer fluid thatincludes the above-described composition or working fluid.

In some embodiments, a method of transferring heat is provided. Themethod includes providing a device; and transferring heat to or from thedevice using a heat transfer fluid that includes the above-describedcomposition or working fluid.

The above summary of the present disclosure is not intended to describeeach embodiment of the present disclosure. The details of one or moreembodiments of the disclosure are also set forth in the descriptionbelow. Other features, objects, and advantages of the disclosure will beapparent from the description and from the claims.

DETAILED DESCRIPTION

In view of an increasing demand for environmentally friendly and lowtoxicity chemical compounds, it is recognized that there exists anongoing need for new working fluids that provide further reductions inenvironmental impact and toxicity, and which can meet the performancerequirements (e.g., nonflammability, solvency, stability, and operatingtemperature range) of a variety of different applications (e.g., heattransfer, two-phase immersion cooling, foam blowing agents, solventcleaning, deposition coating solvents, and electrolyte solvents andadditives), and be manufactured cost-effectively.

Generally, the present disclosure relates to propenylamine compoundsthat include at least one catenary nitrogen atom and are highly enrichedin the E (or trans) isomer. The present disclosure also describes highyield methods of making such E-enriched compounds. Surprisingly, it hasbeen discovered that the E-enriched propenylamines have significantlyshorter atmospheric lifetimes compared to the corresponding Z (or cis)isomers or an equilibrium mixture of E and Z isomers and, therefore,have correspondingly lower global warming potentials. The propenylaminesof the present disclosure are also generally non-flammable, have zeroozone depletion potential, and provide low toxicity for safe handling.

As used herein, “catenated heteroatom” means an atom other than carbon(for example, oxygen, nitrogen, or sulfur) that is bonded to at leasttwo carbon atoms in a carbon chain (linear or branched or within a ring)so as to form a carbon-heteroatom-carbon linkage.

As used herein, “fluoro-” (for example, in reference to a group ormoiety, such as in the case of “fluoroalkylene” or “fluoroalkyl” or“fluorocarbon”) or “fluorinated” means (i) partially fluorinated suchthat there is at least one carbon-bonded hydrogen atom, or (ii)perfluorinated.

As used herein, “perfluoro-” (for example, in reference to a group ormoiety, such as in the case of “perfluoroalkylene” or “perfluoroalkyl”or “perfluorocarbon”) or “perfluorinated” means completely fluorinatedsuch that, except as may be otherwise indicated, there are nocarbon-bonded hydrogen atoms replaceable with fluorine.

As used herein, the singular forms “a”, “an”, and “the” include pluralreferents unless the content clearly dictates otherwise. As used in thisspecification and the appended embodiments, the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

As used herein, the recitation of numerical ranges by endpoints includesall numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.8, 4, and 5).

Unless otherwise indicated, all numbers expressing quantities oringredients, measurement of properties and so forth used in thespecification and embodiments are to be understood as being modified inall instances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the foregoingspecification and attached listing of embodiments can vary dependingupon the desired properties sought to be obtained by those skilled inthe art utilizing the teachings of the present disclosure. At the veryleast, and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claimed embodiments, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

In some embodiments, the present disclosure is directed topropenylamines of general formula (1).

The propenylamines of general formula (1) can exist in one of twoisomeric forms, the E or Z isomer, which are depicted below in generalformulas (1A) and 1(B), respectively.

Surprisingly, it has been discovered that the E-isomer [general formula(1A)] has a significantly shorter atmospheric lifetime than the Z isomer[Structure (1 B)], and correspondingly lower global warming potential(GWP). Therefore, it is advantageous, from an environmentalsustainability standpoint, if the propenylamines could be enriched inthe lower GWP E-isomer (thus reducing the average GWP of the mixture).

In some embodiments, the present disclosure is further directed tomethods of making the above-described E-isomer enriched propenylaminesof general formula (1). However, heretofore, this has not been possible,since all known methods of preparing such propenylamines lead to amixture of E and Z isomers, with the thermodynamically more stable Zisomer generally present as the major isomer. Additionally, knownprocesses designed to isomerize the E and Z isomers would tend to favorthe thermodynamically more stable Z isomer. Still further, the boilingpoints of the E and Z isomers are typically very similar (within a fewdegrees C. or less of each other), thus making separation bydistillation either impossible or impractical for achieving anysignificant level of enrichment of the E isomer. The present disclosureprovides a solution to this problem in that it broadly describespropenylamines that are highly enriched in the thermodynamically lessstable E isomer and high yield methods for preparing such E-enrichedmixtures without sacrificing overall yield and avoiding the need todispose of the less desirable Z isomer.

In some embodiments, the present disclosure is directed to compositionsthat include the propenylamines of general formula (1), wherein at least60 wt. %, 70% wt. %, 80 wt. %, 90 wt. %, 95 wt. % or 98 wt. % of thepropenylamines are in the form of the E isomer (formula 1A) (theremainder being the Z isomer (formula 1B)), based on the total weight ofthe propenylamines of general formula (1) in the composition.

In illustrative embodiments, R_(f1) and R_(f2) in general formula (1)may be, independently, linear or branched perfluoroalkyl groups having1-8 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms. In furtherembodiments, R_(f1) and R_(f2) may be bonded together to form a ringstructure having 4-8 carbon atoms, 4-6 carbon atoms, or 4 carbon atoms.Optionally, R_(f1) and R_(f2) may include one or more catenatedheteroatoms. In some embodiments, if R_(f1) and R_(f2) are bondedtogether to form a ring structure that comprises a second nitrogenheteroatom, said second nitrogen heteroatom may be tertiary and may bebonded to a perfluoroalkyl group having 1-3 or 2-3 carbon atoms.

In various embodiments, representative examples of the compounds ofgeneral formula (1) include the following:

In some embodiments, the E isomer enriched propenylamine compounds ofthe present disclosure may be hydrophobic, relatively chemicallyunreactive, and thermally stable. As discussed above, the E isomerenriched propenylamine compounds may have a low environmental impact. Inthis regard, the E isomer enriched 1-propenylamine compounds may have aglobal warming potential (GWP, over 100 year ITH)) of less than 500,300, 200, 100, 80, or less than 60. As used herein, GWP is a relativemeasure of the global warming potential of a compound based on thestructure of the compound. The GWP of a compound, as defined by theIntergovernmental Panel on Climate Change (IPCC) in 1990 and updated in2007, is calculated as the warming due to the release of 1 kilogram of acompound relative to the warming due to the release of 1 kilogram of CO₂over a specified integration time horizon (ITH).

$\ {{{GWP}_{i}( t^{\prime} )} = {\frac{\overset{ITH}{\int\limits_{0}}{{a_{i}\lbrack {C(t)} \rbrack}{dt}}}{\overset{ITH}{\int\limits_{0}}{{a_{{CO}_{2}}\lbrack {C_{{CO}_{2}}(t)} \rbrack}{dt}}} = \frac{\overset{ITH}{\int\limits_{0}}{a_{i}C_{oi}e^{{- t}/\tau_{i}}{dt}}}{\overset{ITH}{\int\limits_{0}}{{a_{{CO}_{2}}\lbrack {C_{{CO}_{2}}(t)} \rbrack}{dt}}}}}$

In this equation ad is the radiative forcing per unit mass increase of acompound in the atmosphere (the change in the flux of radiation throughthe atmosphere due to the IR absorbance of that compound), C is theatmospheric concentration of a compound, τ is the atmospheric lifetimeof a compound, t is time, and i is the compound of interest. Thecommonly accepted ITH is 100 years representing a compromise betweenshort-term effects (20 years) and longer-term effects (500 years orlonger). The concentration of an organic compound, i, in the atmosphereis assumed to follow pseudo first order kinetics (i.e., exponentialdecay). The concentration of CO₂ over that same time intervalincorporates a more complex model for the exchange and removal of CO₂from the atmosphere (the Bern carbon cycle model).

The perfluorinated propenyl amines of general formula (1) can beprepared by electrochemical perfluorination of the appropriate nitrogencontaining hydrocarbon carboxylate derivatives followed bydecarboxylation of the perfluorinated nitrogen-containing carboxylates,carbonyl fluorides, or esters using procedures that are well known inthe art, including those described in T. Abe, JP 01070444A; T. Abe, JP0107445A; or M. Bulinski, WO 2015/095285, which are herein incorporatedby reference in their entirety. However, as discussed above, suchmethods yield a mixture of perfluorinated E- and Z 1-propenylamines inwhich the thermodynamically preferred Z isomer is the major component.

In some embodiments, the present disclosure is directed to high yieldand selective methods of synthesizing the propenyl amines of generalformula (1) that are enriched in the E isomer, without resorting toimpractical separation methods and the cost and waste associated withdisposal of the higher GWP Z isomer. In some embodiments, the methodincludes selectively isomerizing a perfluorinated allylamine of generalformula (2) over an isomerization catalyst to predominantly form theE-1-propenylamine of general formula (1A), while avoiding significantformation of the thermodynamically more stable Z-1-propenylamine ofgeneral formula (1B).

In some embodiments, the synthesis methods of the present disclosure mayinclude a catalytic isomerization process which provides a mechanism forisomerizing a perfluorinated allylamine of general structure (2) to thecorresponding E-1-propenylamine of general structure (1A) with asurprisingly high degree of selectivity. In some embodiments, theprocess may include catalytically isomerizing the terminal olefin of theperfluorinated allylamine to the corresponding internal olefin, with asurprisingly strong preference for the E (vs. Z) internal olefin isomer(even though the Z isomer is the thermodynamically more stable isomer).

In some embodiments, the catalytic isomerization process may bedescribed by the reaction shown in Scheme 1, in which the E-1-propenylamine is the major isomerization product and the Z-1-propenylamine isthe minor isomerization product.

In some embodiments, catalysts for use in the catalytic isomerizationprocess shown in Scheme 1 may include Lewis acidic metal fluorides andmetalloid fluorides including, for example, any or all of TiF₄, ZrF₄,NbF₅, TaF₅, BF₃, SbF₅. In various embodiments, the catalyst may includeany or all of TiF₄, NbF₅, TaF₅, and SbF₅. In some embodiments, thecatalyst may include any or all of NbF₅ and TaF₅. In illustrativeembodiments, in addition or as an alternative to the aforementionedcatalysts, catalysts suitable for use in the methods of the presentdisclosure may include certain other fluorinated Lewis acids (includingperfluorinated Lewis acids and certain Lewis acid mixedchlorofluorides), such as any or all of ACF (aluminum chlorofluoride),rare earth metal fluorides (including lanthanide and actinide metalfluorides), antimony chlorofluorides (including SbCl₂F₃ and SbCl₄F), aswell as the Bronsted acid, HSbF₆. In other embodiments, the catalyst mayinclude Lewis acidic metal chlorides and metalloid chlorides, including,for example, any or all of AlCl₃, SbCl₅, TiCl₄, and the like. It isbelieved that the latter Lewis acid catalysts form mixed chlorofluoridesin situ via a halogen exchange reaction with the starting fluorinatedallyl amine and it is these mixed chlorofluorides that are the activeisomerization catalysts. Surprisingly, it was discovered that the Lewisacidic metal chlorides and metalloid chlorides are as effective as theirfluoride counterparts, which is significant because the chlorides may beobtained at an appreciably lower materials cost. The Lewis acidic metaland metalloid fluorides, chlorofluorides, and chlorides useful ascatalysts in the processes of the present disclosure may be chosen fromgroups 3 through 15 of the periodic table (modern IUPAC convention),including the lanthanide and actinides series. In one embodiment thecatalysts are chosen from groups 4, 5, 13, and 15 of the periodic table.

In some embodiments, the reaction described in Scheme 1 may be carriedout neat (i.e., in the absence of solvent), although inert solvents suchas perfluorinated hydrocarbons may also be employed, if desired.Reaction temperature and reaction time may be selected based on thecatalyst employed. For example, with some catalysts, low temperatures(e.g., 0° C.) and short reaction times (e.g., — 1 hr) may be employed,because at higher temperatures the catalyst will catalyze E/Zisomerization, thus resulting in a loss of selectivity. As an additionalexample, reaction temperatures between 20-100° C. and higher may beemployed to increase the rates of reaction such that the isomerizationreaction is complete or nearly complete in a period of approximately1-20 hours or less. When using the catalysts of the present disclosure,the catalytic isomerization process of Scheme 1 may proceed withnegligible side reactions, thus no or relatively few (less than 5%, 3%,2%, or 1% by weight) detectable side products are formed, which mightotherwise contaminate the propenylamine product.

In some embodiments, the perfluorinated allylamines of general formula(2) may be prepared by methods that are well known in the art, includingthose methods described in T. Abe, JP 01070444A; and T. Abe, JP0107445A, both of which are incorporated herein by reference in theirentirety and described in Scheme 2 The first step consists of a Michaeladdition of a secondary amine (RH¹(RH²)NH) to methyl methacrylate. Therespective beta-aminoesters undergoe electrochemical fluorination toafford the desired perfluorinated acid fluoride intermediates which aresubjected to thermolysis in the presence of Na₂CO₃ to give a mixture ofperfluorinated allylic amines and perfluorinated 1-aminopropenes. Thedesired perfluorinated allyl amine products can be purified bydistillation and have been used in pure form for fluoropolymer synthesis(Y. Hayakawa et al. Polymer 1995, 36, 2807) and for additions bybis(trifluoromethyl)amino-oxyl reagent (G. Newsholme et al. J. FluorineChem. 1994, 69, 163).

In some embodiments, the present disclosure is further directed toworking fluids that include the above-described propenylamine compoundsas a major component. For example, the working fluids may include atleast 25%, at least 50%, at least 70%, at least 80%, at least 90%, atleast 95%, or at least 99% by weight of the above-describedpropenylamine compounds based on the total weight of the working fluid.In addition to the propenylamine compounds, the working fluids mayinclude a total of up to 75%, up to 50%, up to 30%, up to 20%, up to10%, or up to 5% by weight of one or more of the following components:alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons,perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters,ketones, oxiranes, aromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins,hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, ormixtures thereof, based on the total weight of the working fluid. Suchadditional components can be chosen to modify or enhance the propertiesof a composition for a particular use.

In some embodiments, the present disclosure is further directed to anapparatus for heat transfer that includes a device and a mechanism fortransferring heat to or from the device. The mechanism for transferringheat may include a heat transfer working fluid that includes a1-propenylamine compound of the present disclosure.

The provided apparatus for heat transfer may include a device. Thedevice may be a component, work-piece, assembly, etc. to be cooled,heated or maintained at a predetermined temperature or temperaturerange. Such devices include electrical components, mechanical componentsand optical components. Examples of devices of the present disclosureinclude, but are not limited to microprocessors, wafers used tomanufacture semiconductor devices, power control semiconductors,electrical distribution switch gear, power transformers, circuit boards,multi-chip modules, packaged and unpackaged semiconductor devices,lasers, chemical reactors, fuel cells, heat exchangers, andelectrochemical cells. In some embodiments, the device can include achiller, a heater, or a combination thereof.

In yet other embodiments, the devices can include electronic devices,such as processors, including microprocessors. As these electronicdevices become more powerful, the amount of heat generated per unit timeincreases. Therefore, the mechanism of heat transfer plays an importantrole in processor performance. The heat-transfer fluid typically hasgood heat transfer performance, good electrical compatibility (even ifused in “indirect contact” applications such as those employing coldplates), as well as low toxicity, low (or non-) flammability and lowenvironmental impact. Good electrical compatibility suggests that theheat-transfer fluid candidate exhibit high dielectric strength, highvolume resistivity, and poor solvency for polar materials. Additionally,the heat-transfer fluid should exhibit good mechanical compatibility,that is, it should not affect typical materials of construction in anadverse manner.

The provided apparatus may include a mechanism for transferring heat.The mechanism may include a heat transfer fluid. The heat transfer fluidmay include one or more 1-propenylamine compounds of the presentdisclosure. Heat may be transferred by placing the heat transfermechanism in thermal contact with the device. The heat transfermechanism, when placed in thermal contact with the device, removes heatfrom the device or provides heat to the device, or maintains the deviceat a selected temperature or temperature range. The direction of heatflow (from device or to device) is determined by the relativetemperature difference between the device and the heat transfermechanism.

The heat transfer mechanism may include facilities for managing theheat-transfer fluid, including, but not limited to pumps, valves, fluidcontainment systems, pressure control systems, condensers, heatexchangers, heat sources, heat sinks, refrigeration systems, activetemperature control systems, and passive temperature control systems.Examples of suitable heat transfer mechanisms include, but are notlimited to, temperature controlled wafer chucks in plasma enhancedchemical vapor deposition (PECVD) tools, temperature-controlled testheads for die performance testing, temperature-controlled work zoneswithin semiconductor process equipment, thermal shock test bath liquidreservoirs, and constant temperature baths. In some systems, such asetchers, ashers, PECVD chambers, vapor phase soldering devices, andthermal shock testers, the upper desired operating temperature may be ashigh as 170° C., as high as 200° C., or even as high as 230° C.

Heat can be transferred by placing the heat transfer mechanism inthermal contact with the device. The heat transfer mechanism, whenplaced in thermal contact with the device, removes heat from the deviceor provides heat to the device, or maintains the device at a selectedtemperature or temperature range. The direction of heat flow (fromdevice or to device) is determined by the relative temperaturedifference between the device and the heat transfer mechanism. Theprovided apparatus can also include refrigeration systems, coolingsystems, testing equipment and machining equipment. In some embodiments,the provided apparatus can be a constant temperature bath or a thermalshock test bath.

In some embodiments, the present disclosure is directed to a fireextinguishing composition. The composition may include one or morepropenylamine compounds of the present disclosure and one or moreco-extinguishing agents.

In illustrative embodiments, the co-extinguishing agent may includehydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,hydrobromocarbons, iodofluorocarbons, fluorinated ketones,hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones,hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinatedsulfones, fluorinated vinylethers, unsaturated fluoro-ethers,bromofluoroolefins, chlorofluorolefins, iodofluoroolefins, fluorinatedvinyl amines, fluorinated aminopropenes and mixtures thereof.

Such co-extinguishing agents can be chosen to enhance the extinguishingcapabilities or modify the physical properties (e.g., modify the rate ofintroduction by serving as a propellant) of an extinguishing compositionfor a particular type (or size or location) of fire and can preferablybe utilized in ratios (of co-extinguishing agent to propenylaminecompound) such that the resulting composition does not form flammablemixtures in air.

In some embodiments, the propenylamine compounds and theco-extinguishing agent may be present in the fire extinguishingcomposition in amounts sufficient to suppress or extinguish a fire. Thepropenylamine compounds and the co-extinguishing agent can be in aweight ratio of from about 9:1 to about 1:9.

In some embodiments, the present disclosure is directed to an apparatusfor converting thermal energy into mechanical energy in a Rankine cycle.The apparatus may include a working fluid that includes one or morepropenylamine compounds of the present disclosure. The apparatus mayfurther include a heat source to vaporize the working fluid and form avaporized working fluid, a turbine through which the vaporized workingfluid is passed thereby converting thermal energy into mechanicalenergy, a condenser to cool the vaporized working fluid after it ispassed through the turbine, and a pump to recirculate the working fluid.

In some embodiments, the present disclosure relates to a process forconverting thermal energy into mechanical energy in a Rankine cycle. Theprocess may include using a heat source to vaporize a working fluid thatincludes one or more propenylamine compounds of the present disclosureto form a vaporized working fluid. In some embodiments, the heat istransferred from the heat source to the working fluid in an evaporatoror boiler. The vaporized working fluid may pressurized and can be usedto do work by expansion. The heat source can be of any form such as fromfossil fuels, e.g., oil, coal, or natural gas. Additionally, in someembodiments, the heat source can come from nuclear power, solar power,or fuel cells. In other embodiments, the heat can be “waste heat” fromother heat transfer systems that would otherwise be lost to theatmosphere. The “waste heat,” in some embodiments, can be heat that isrecovered from a second Rankine cycle system from the condenser or othercooling device in the second Rankine cycle.

An additional source of “waste heat” can be found at landfills wheremethane gas is flared off. In order to prevent methane gas from enteringthe environment and thus contributing to global warming, the methane gasgenerated by the landfills can be burned by way of “flares” producingcarbon dioxide and water which are both less harmful to the environmentin terms of global warming potential than methane. Other sources of“waste heat” that can be useful in the provided processes are geothermalsources and heat from other types of engines such as gas turbine enginesthat give off significant heat in their exhaust gases and to coolingliquids such as water and lubricants.

In the provided process, the vaporized working fluid may expanded thougha device that can convert the pressurized working fluid into mechanicalenergy. In some embodiments, the vaporized working fluid is expandedthrough a turbine which can cause a shaft to rotate from the pressure ofthe vaporized working fluid expanding. The turbine can then be used todo mechanical work such as, in some embodiments, operate a generator,thus generating electricity. In other embodiments, the turbine can beused to drive belts, wheels, gears, or other devices that can transfermechanical work or energy for use in attached or linked devices.

After the vaporized working fluid has been converted to mechanicalenergy the vaporized (and now expanded) working fluid can be condensedusing a cooling source to liquefy for reuse. The heat released by thecondenser can be used for other purposes including being recycled intothe same or another Rankine cycle system, thus saving energy. Finally,the condensed working fluid can be pumped by way of a pump back into theboiler or evaporator for reuse in a closed system.

The desired thermodynamic characteristics of organic Rankine cycleworking fluids are well known to those of ordinary skill and arediscussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274(Zyhowski et al.). The greater the difference between the temperature ofthe heat source and the temperature of the condensed liquid or aprovided heat sink after condensation, the higher the Rankine cyclethermodynamic efficiency. The thermodynamic efficiency is influenced bymatching the working fluid to the heat source temperature. The closerthe evaporating temperature of the working fluid to the sourcetemperature, the higher the efficiency of the system. Toluene can beused, for example, in the temperature range of 79° C. to about 260° C.,however toluene has toxicological and flammability concerns. Fluids suchas 1,1-dichloro-2,2,2-trifluoroethane and 1,1,1,3,3-pentafluoropropanecan be used in this temperature range as an alternative. But1,1-dichloro-2,2,2-trifluoroethane can form toxic compounds below 300°C. and need to be limited to an evaporating temperature of about 93° C.to about 121° C. Thus, there is a desire for otherenvironmentally-friendly Rankine cycle working fluids with highercritical temperatures so that source temperatures such as gas turbineand internal combustion engine exhaust can be better matched to theworking fluid.

In some embodiments, the present disclosure relates to the use of thepropenylamine compounds of the present disclosure as nucleating agentsin the production of polymeric foams and in particular in the productionof polyurethane foams and phenolic foams. In this regard, in someembodiments, the present disclosure is directed to a foamablecomposition that includes one or more blowing agents, one or morefoamable polymers or precursor compositions thereof, and one or morenucleating agents that include a 1-propenylamine compound of the presentdisclosure.

In some embodiments, a variety of blowing agents may be used in theprovided foamable compositions including liquid or gaseous blowingagents that are vaporized in order to foam the polymer or gaseousblowing agents that are generated in situ in order to foam the polymer.Illustrative examples of blowing agents include hydrochlorofluorocarbons(HCFCs), hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs),iodofluorocarbons (IFCs), hydrocarbons, hydrofluoroolefins (HFOs) andhydrofluoroethers (HFEs). The blowing agent for use in the providedfoamable compositions can have a boiling point of from about −45° C. toabout 100° C. at atmospheric pressure. Typically, at atmosphericpressure the blowing agent has a boiling point of at least about 15° C.,more typically between about 20° C. and about 80° C. The blowing agentcan have a boiling point of between about 30° C. and about 65° C.Further illustrative examples of blowing agents that can be used includealiphatic and cycloaliphatic hydrocarbons having about 5 to about 7carbon atoms, such as n-pentane and cyclopentane, esters such as methylformate, HFCs such as CF₃CF₂CHFCHFCF₃, CF₃CH₂CF₂H, CF₃CH₂CF₂CH₃,CF₃CF₂H, CH₃CF₂H(HFC-152a), CF₃CH₂CH₂CF₃ and CHF₂CF₂CH₂F, HCFCs such asCH₃CCl₂F, CF₃CHCl₂, and CF₂HCl, HCCs such as 2-chloropropane, and IFCssuch as CF₃I, and HFEs such as C₄F₉OCH₃ and HFOs such as CF₃CF=CH₂,CF₃CH═CHF, CF₃CH═CHCl, and CF₃CH═CHCF₃ In certain formulations CO₂generated from the reaction of water with foam precursor such as anisocyanate can be used as a blowing agent.

In various embodiments, the provided foamable composition may alsoinclude one or more foamable polymers or a precursor compositionthereof. Foamable polymers suitable for use in the provided foamablecompositions include, for example, polyolefins, e.g., polystyrene,poly(vinyl chloride), and polyethylene. Foams can be prepared fromstyrene polymers using conventional extrusion methods. The blowing agentcomposition can be injected into a heat-plastified styrene polymerstream within an extruder and admixed therewith prior to extrusion toform foam. Representative examples of suitable styrene polymers include,for example, the solid homopolymers of styrene, α-methylstyrene,ring-alkylated styrenes, and ring-halogenated styrenes, as well ascopolymers of these monomers with minor amounts of other readilycopolymerizable olefinic monomers, e.g., methyl methacrylate,acrylonitrile, maleic anhydride, citraconic anhydride, itaconicanhydride, acrylic acid, N-vinylcarbazole, butadiene, anddivinylbenzene. Suitable vinyl chloride polymers include, for example,vinyl chloride homopolymer and copolymers of vinyl chloride with othervinyl monomers. Ethylene homopolymers and copolymers of ethylene with,e.g., 2-butene, acrylic acid, propylene, or butadiene may also beuseful. Mixtures of different types of polymers can be employed.

In various embodiments, the foamable compositions of the presentdisclosure may have a molar ratio of nucleating agent to blowing agentof no more than 1:50, 1:25, 1:9, or 1:7, 1:3, or 1:2.

Other conventional components of foam formulations can, optionally, bepresent in the foamable compositions of the present disclosure. Forexample, cross-linking or chain-extending agents, foam-stabilizingagents or surfactants, catalysts and fire-retardants can be utilized.Other possible components include fillers (e.g., carbon black),colorants, fungicides, bactericides, antioxidants, reinforcing agents,antistatic agents, and other additives or processing aids.

In some embodiments, polymeric foams can be prepared by vaporizing atleast one liquid or gaseous blowing agent or generating at least onegaseous blowing agent in the presence of at least one foamable polymeror a precursor composition thereof and a nucleating agent as describedabove. In further embodiments, polymeric foams can be prepared using theprovided foamable compositions by vaporizing (e.g., by utilizing theheat of precursor reaction) at least one blowing agent in the presenceof a nucleating agent as described above, at least one organicpolyisocyanate and at least one compound containing at least tworeactive hydrogen atoms. In making a polyisocyanate-based foam, thepolyisocyanate, reactive hydrogen-containing compound, and blowing agentcomposition can generally be combined, thoroughly mixed (using, e.g.,any of the various known types of mixing head and spray apparatus), andpermitted to expand and cure into a cellular polymer. It is oftenconvenient, but not necessary, to preblend certain of the components ofthe foamable composition prior to reaction of the polyisocyanate and thereactive hydrogen-containing compound. For example, it is often usefulto first blend the reactive hydrogen-containing compound, blowing agentcomposition, and any other components (e.g., surfactant) except thepolyisocyanate, and to then combine the resulting mixture with thepolyisocyanate. Alternatively, all components of the foamablecomposition can be introduced separately. It is also possible topre-react all or a portion of the reactive hydrogen-containing compoundwith the polyisocyanate to form a prepolymer.

In some embodiments, the present disclosure is directed to dielectricfluids that include one or more propenylamine compounds of the presentdisclosure, as well as to electrical devices (e.g., capacitors,switchgear, transformers, or electric cables or buses) that include suchdielectric fluids. For purposes of the present application, the term“dielectric fluid” is inclusive of both liquid dielectrics and gaseousdielectrics. The physical state of the fluid, gaseous or liquid, isdetermined at the operating conditions of temperature and pressure ofthe electrical device in which it is used.

In some embodiments, the dielectric fluids include one or morepropenylamine compounds of the present disclosure and, optionally, oneor more second dielectric fluids. Suitable second dielectric fluidsinclude, for example, air, nitrogen, helium, argon, and carbon dioxide,or combinations thereof. The second dielectric fluid may be anon-condensable gas or an inert gas. Generally, the second dielectricfluid may be used in amounts such that vapor pressure is at least 70 kPaat 25° C., or at the operating temperature of the electrical device.

The dielectric fluids of the present application are useful forelectrical insulation and for arc quenching and current interruptionequipment used in the transmission and distribution of electricalenergy. Generally, there are three major types of electrical devices inwhich the fluids of the present disclosure can be used: (1)gas-insulated circuit breakers and current-interruption equipment, (2)gas-insulated transmission lines, and (3) gas-insulated transformers.Such gas-insulated equipment is a major component of power transmissionand distribution systems.

In some embodiments, the present disclosure provides electrical devices,such as capacitors, comprising metal electrodes spaced from each othersuch that the gaseous dielectric fills the space between the electrodes.The interior space of the electrical device may also comprise areservoir of the liquid dielectric fluid which is in equilibrium withthe gaseous dielectric fluid. Thus, the reservoir may replenish anylosses of the dielectric fluid.

In some embodiments, the present disclosure relates to coatingcompositions that include a solvent composition that one or morepropenylamine compounds of the present disclosure, and one or morecoating materials which are soluble or dispersible in the solventcomposition.

In various embodiments, the coating materials of the coatingcompositions may include pigments, lubricants, stabilizers, adhesives,anti-oxidants, dyes, polymers, pharmaceuticals, release agents,inorganic oxides, and the like, and combinations thereof. For example,coating materials may include perfluoropolyether, hydrocarbon, andsilicone lubricants; amorphous copolymers of tetrafluoroethylene;polytetrafluoroethylene; or combinations thereof. Further examples ofsuitable coating materials include titanium dioxide, iron oxides,magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid,acrylic adhesives, polytetrafluoroethylene, amorphous copolymers oftetrafluoroethylene, or combinations thereof.

In some embodiments, the above-described coating compositions can beuseful in coating deposition, where the propenylamine compounds functionas a carrier for a coating material to enable deposition of the materialon the surface of a substrate. In this regard, the present disclosurefurther relates to a process for depositing a coating on a substratesurface using the coating composition. The process comprises the step ofapplying to at least a portion of at least one surface of a substrate acoating of a liquid coating composition comprising (a) a solventcomposition containing one or more of the 1-propenylamine compounds; and(b) one or more coating materials which are soluble or dispersible inthe solvent composition. The solvent composition can further compriseone or more co-dispersants or co-solvents and/or one or more additives(e.g., surfactants, coloring agents, stabilizers, anti-oxidants, flameretardants, and the like). Preferably, the process further comprises thestep of removing the solvent composition from the coating by, e.g.,allowing evaporation (which can be aided by the application of, e.g.,heat or vacuum).

In various embodiments, to form a coating composition, the components ofthe coating composition (i.e., the propenylamine compound(s), thecoating material(s), and any co-dispersant(s) or co-solvent(s) utilized)can be combined by any conventional mixing technique used fordissolving, dispersing, or emulsifying coating materials, e.g., bymechanical agitation, ultrasonic agitation, manual agitation, and thelike. The solvent composition and the coating material(s) can becombined in any ratio depending upon the desired thickness of thecoating. For example, the coating material(s) may constitute from about0.1 to about 10 weight percent of the coating composition.

In illustrative embodiments, the deposition process of the disclosurecan be carried out by applying the coating composition to a substrate byany conventional technique. For example, the composition can be brushedor sprayed (e.g., as an aerosol) onto the substrate, or the substratecan be spin-coated. In some embodiments, the substrate may be coated byimmersion in the composition. Immersion can be carried out at anysuitable temperature and can be maintained for any convenient length oftime. If the substrate is a tubing, such as a catheter, and it isdesired to ensure that the composition coats the lumen wall, thecomposition may be drawn into the lumen by the application of reducedpressure.

In various embodiments, after a coating is applied to a substrate, thesolvent composition can be removed from the coating (e.g., byevaporation). If desired, the rate of evaporation can be accelerated byapplication of reduced pressure or mild heat. The coating can be of anyconvenient thickness, and, in practice, the thickness will be determinedby such factors as the viscosity of the coating material, thetemperature at which the coating is applied, and the rate of withdrawal(if immersion is utilized).

Both organic and inorganic substrates can be coated by the processes ofthe present disclosure. Representative examples of the substratesinclude metals, ceramics, glass, polycarbonate, polystyrene,acrylonitrile-butadiene-styrene copolymer, natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool, synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof, fabrics including a blend of natural andsynthetic fibers, and composites of the foregoing materials. In someembodiments, substrates that may be coated include, for example,magnetic hard disks or electrical connectors with perfluoropolyetherlubricants or medical devices with silicone lubricants.

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more propenylamine compounds of thepresent disclosure, and one or more co-solvents.

In some embodiments, the propenylamine compounds may be present in anamount greater than 50 weight percent, greater than 60 weight percent,greater than 70 weight percent, or greater than 80 weight percent basedupon the total weight of the propenylamine compounds and theco-solvent(s).

In various embodiments, the cleaning composition may further comprise asurfactant. Suitable surfactants include those surfactants that aresufficiently soluble in the fluorinated olefin, and which promote soilremoval by dissolving, dispersing or displacing the soil. One usefulclass of surfactants are those nonionic surfactants that have ahydrophilic-lipophilic balance (HLB) value of less than about 14.Examples include ethoxylated alcohols, ethoxylatedalkyl phenols,ethoxylated fatty acids, alkylarysulfonates, glycerol esters,ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures ofsurfactants having complementary properties may be used in which onesurfactant is added to the cleaning composition to promote oily soilremoval and another added to promote water-soluble oil removal. Thesurfactant, if used, can be added in an amount sufficient to promotesoil removal. Typically, surfactant is added in amounts from about 0.1to 5.0 wt. %, preferably in amounts from about 0.2 to 2.0 wt. % of thecleaning composition.

In illustrative embodiments, the co-solvent may include alcohols,ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinatedtertiary amines, perfluoroethers, cycloalkanes, esters, ketones,oxiranes, aromatics, haloaromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins,hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, ormixtures thereof. Representative examples of co-solvents which can beused in the cleaning composition include methanol, ethanol, isopropanol,t-butyl alcohol, methyl t-butyl ether, methyl t-amyl ether,1,2-dimethoxyethane, cyclohexane, 2,2,4-trimethylpentane, n-decane,terpenes (e.g., a-pinene, camphene, and limonene),trans-1,2-dichloroethylene, cis-1,2-dichloroethylene,methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethylacetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone,naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene,bis(trifluoromethyl)benzenes, hexamethyl disiloxane, octamethyltrisiloxane, perfluorohexane, perfluoroheptane, perfluorooctane,perfluorotributylamine, perfluoro-N-methyl morpholine, perfluoro-2-butyloxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane,1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane,1,1,1,2,2-pentafluoro-3,3-dichloropropane,1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane,1,1,1,2,2,4-hexafluorobutane,1-trifluoromethyl-1,2,2-trifluorocyclobutane,3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane,or mixtures thereof.

In some embodiments, the present disclosure relates to a process forcleaning a substrate. The cleaning process can be carried out bycontacting a contaminated substrate with a cleaning composition asdiscussed above. The propenylamine compounds can be utilized alone or inadmixture with each other or with other commonly-used cleaning solvents,e.g., alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons,perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters,ketones, oxiranes, aromatics, haloaromatics, siloxanes,hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons,hydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins,hydrofluoroethers, or mixtures thereof. Such co-solvents can be chosento modify or enhance the solvency properties of a cleaning compositionfor a particular use and can be utilized in ratios (of co-solvent to1-propenylamine compounds) such that the resulting composition has noflash point. If desirable for a particular application, the cleaningcomposition can further contain one or more dissolved or dispersedgaseous, liquid, or solid additives (for example, carbon dioxide gas,surfactants, stabilizers, antioxidants, or activated carbon).

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more propenylamine compounds of thepresent disclosure and optionally one or more surfactants. Suitablesurfactants include those surfactants that are sufficiently soluble inthe propenylamine compounds, and which promote soil removal bydissolving, dispersing or displacing the soil. One useful class ofsurfactants are those nonionic surfactants that have ahydrophilic-lipophilic balance (HLB) value of less than about 14.Examples include ethoxylated alcohols, ethoxylated alkylphenols,ethoxylated fatty acids, alkylaryl sulfonates, glycerol esters,ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures ofsurfactants having complementary properties may be used in which onesurfactant is added to the cleaning composition to promote oily soilremoval and another added to promote water-soluble soil removal. Thesurfactant, if used, can be added in an amount sufficient to promotesoil removal. Typically, surfactant may be added in amounts from 0.1 to5.0 wt. % or from 0.2 to 2.0 wt. % of the cleaning composition.

The cleaning processes of the disclosure can also be used to dissolve orremove most contaminants from the surface of a substrate. For example,materials such as light hydrocarbon contaminants; higher molecularweight hydrocarbon contaminants such as mineral oils and greases;fluorocarbon contaminants such as perfluoropolyethers,bromotrifluoroethylene oligomers (gyroscope fluids), andchlorotrifluoroethylene oligomers (hydraulic fluids, lubricants);silicone oils and greases; solder fluxes; particulates; water; and othercontaminants encountered in precision, electronic, metal, and medicaldevice cleaning can be removed.

The cleaning compositions can be used in either the gaseous or theliquid state (or both), and any of known or future techniques for“contacting” a substrate can be utilized. For example, a liquid cleaningcomposition can be sprayed or brushed onto the substrate, a gaseouscleaning composition can be blown across the substrate, or the substratecan be immersed in either a gaseous or a liquid composition. Elevatedtemperatures, ultrasonic energy, and/or agitation can be used tofacilitate the cleaning. Various different solvent cleaning techniquesare described by B. N. Ellis in Cleaning and Contamination ofElectronics Components and Assemblies, Electrochemical PublicationsLimited, Ayr, Scotland, pages 182-94 (1986).

Both organic and inorganic substrates can be cleaned by the processes ofthe present disclosure. Representative examples of the substratesinclude metals; ceramics; glass; polycarbonate; polystyrene;acrylonitrile-butadiene-styrene copolymer; natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool; synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof; fabrics comprising a blend of natural andsynthetic fibers; and composites of the foregoing materials. In someembodiments, the process may be used in the precision cleaning ofelectronic components (e.g., circuit boards), optical or magnetic media,or medical devices.

In some embodiments, the present disclosure further relates toelectrolyte compositions that include one or more propenylaminecompounds of the present disclosure. The electrolyte compositions maycomprise (a) a solvent composition including one or more of the1-propenylamine compounds; and (b) at least one electrolyte salt. Theelectrolyte compositions of the present disclosure exhibit excellentoxidative stability, and when used in high voltage electrochemical cells(such as rechargeable lithium ion batteries) provide outstanding cyclelife and calendar life. For example, when such electrolyte compositionsare used in an electrochemical cell with a graphitized carbon electrode,the electrolytes provide stable cycling to a maximum charge voltage ofat least 4.5V and up to 6.0V vs. Li/Li⁺.

Electrolyte salts that are suitable for use in preparing the electrolytecompositions of the present disclosure include those salts that compriseat least one cation and at least one weakly coordinating anion (theconjugate acid of the anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid (for example, abis(perfluoroalkanesulfonyl)imide anion); that are at least partiallysoluble in a selected propenylamine compound (or in a blend thereof withone or more other propenylamine compounds or one or more conventionalelectrolyte solvents); and that at least partially dissociate to form aconductive electrolyte composition. The salts may be stable over a rangeof operating voltages, are non-corrosive, and are thermally andhydrolytically stable. Suitable cations include alkali metal, alkalineearth metal, Group IIB metal, Group IIIB metal, transition metal, rareearth metal, and ammonium (for example, tetraalkylammonium ortrialkylammonium) cations, as well as a proton. In some embodiments,cations for battery use include alkali metal and alkaline earth metalcations. Suitable anions include fluorine-containing inorganic anionssuch as (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, and SbF₆ ⁻; CIO₄ ⁻; HSO₄ ⁻;H₂PO₄ ⁻; organic anions such as alkane, aryl, and alkaryl sulfonates;fluorine-containing and nonfluorinated tetraarylborates; carboranes andhalogen-, alkyl-, or haloalkylsubstituted carborane anions includingmetallocarborane anions; and fluorine-containing organic anions such asperfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)imides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides; and the like. Preferred anionsfor battery use include fluorine-containing inorganic anions (forexample, (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, and AsF₆ ⁻) and fluorine-containingorganic anions (for example, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides). The fluorine-containing organicanions can be either fully fluorinated, that is perfluorinated, orpartially fluorinated (within the organic portion thereof). In someembodiments, the fluorine-containing organic anion is at least about 80percent fluorinated (that is, at least about 80 percent of thecarbon-bonded substituents of the anion are fluorine atoms). In someembodiments, the anion is perfluorinated (that is, fully fluorinated,where all of the carbon-bonded substituents are fluorine atoms). Theanions, including the perfluorinated anions, can contain one or morecatenary heteroatoms such as, for example, nitrogen, oxygen, or sulfur.In some embodiments, fluorine-containing organic anions includeperfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides.

In some embodiments, the electrolyte salts may include lithium salts.Suitable lithium salts include, for example, lithiumhexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithiumbis(perfluoroethanesulfonyl)imide, lithium tetrafluoroborate, lithiumperchlorate, lithium hexafluoroarsenate, lithiumtrifluoromethanesulfonate, lithiumtris(trifluoromethanesulfonyl)methide, lithium bis(fluorosulfonyl)imide(Li-FSI), and mixtures of two or more thereof.

The electrolyte compositions of the present disclosure can be preparedby combining at least one electrolyte salt and a solvent compositionincluding at least one propenylamine compound of the present disclosure,such that the salt is at least partially dissolved in the solventcomposition at the desired operating temperature. The propenylaminecompounds (or a normally liquid composition including, consisting, orconsisting essentially thereof) can be used in such preparation.

In some embodiments, the electrolyte salt is employed in the electrolytecomposition at a concentration such that the conductivity of theelectrolyte composition is at or near its maximum value (typically, forexample, at a Li molar concentration of around 0.1-4.0 M, or 1.0-2.0 M,for electrolytes for lithium batteries), although a wide range of otherconcentrations may also be employed.

In some embodiments, one or more conventional electrolyte solvents aremixed with the propenylamine compound(s) (for example, such that thepropenylamine(s) constitute from about 1 to about 80 or 90 percent ofthe resulting solvent composition). Useful conventional electrolytesolvents include, for example, organic and fluorine-containingelectrolyte solvents (for example, propylene carbonate, ethylenecarbonate, dimethyl carbonate, diethyl carbonate, ethyl methylcarbonate, dimethoxyethane, 7-butyrolactone, diglyme (that is,diethylene glycol dimethyl ether), tetraglyme (that is, tetraethyleneglycol dimethyl ether), monofluoroethylene carbonate, vinylenecarbonate, ethyl acetate, methyl butyrate, tetrahydrofuran,alkyl-substituted tetrahydrofuran, 1,3-dioxolane, alkyl-substituted1,3-dioxolane, tetrahydropyran, alkyl-substituted tetrahydropyran, andthe like, and mixtures thereof). Other conventional electrolyteadditives (for example, a surfactant) can also be present, if desired.

The present disclosure further relates to electrochemical cells (e.g.,fuel cells, batteries, capacitors, electrochromic windows) that includethe above-described electrolyte compositions. Such an electrochemicalcell may include a positive electrode, a negative electrode, aseparator, and the above-described electrolyte composition.

A variety of negative and positive electrodes may be employed in theelectrochemical cells. Representative negative electrodes includegraphitic carbons e.g., those having a spacing between (002)crystallographic planes, d₀₀₂, of 3.45 A>d_(002>3.354) A and existing informs such as powders, flakes, fibers or spheres (e.g., mesocarbonmicrobeads); Li_(4/3)Ti_(5/3)O₄ the lithium alloy compositions describedin U. S. Pat. No. 6,203,944 (Turner ‘944) entitled “ELECTRODE FOR ALITHIUM BATTERY” and PCT Published Patent Application No. WO 00103444(Turner PCT) entitled “ELECTRODE MATERIAL AND COMPOSITIONS”; andcombinations thereof. Representative positive electrodes includeLiFePO₄, LiMnPO₄, LiCoPO₄, LiMn₂O₄, LiCoO₂ and combinations thereof. Thenegative or positive electrode may contain additives such as will befamiliar to those skilled in the art, e. g., carbon black for negativeelectrodes and carbon black, flake graphite and the like for positiveelectrodes.

The electrochemical devices of the present disclosure can be used invarious electronic articles such as computers, power tools, automobiles,telecommunication devices, and the like.

Embodiments

1. A composition comprising a perfluorinated propenylamine representedby the following general formula (1):

wherein each occurrence of R_(f1) and R_(f2) is:

-   -   (i) independently a linear or branched perfluoroalkyl group        having 1-8 carbon atoms and optionally comprises one or more        catenated heteroatoms; or    -   (ii) bonded together to form a ring structure having 4-8 carbon        atoms and that optionally comprises one or more catenated        heteroatoms; and

wherein at least 60 wt. % of the perfluorinated propenylamine is in theform of the E isomer, based on the total weight of the perfluorinatedpropenylamine in the composition.

2. The composition of embodiment 1, wherein at least 70 wt. % of theperfluorinated propenylamine is in the form of the E isomer, based onthe total weight of the perfluorinated propenylamine in the composition.3. The composition of any one of embodiments 1-2, wherein eachoccurrence of R_(f1) and R_(f2) is independently a linear or branchedperfluoroalkyl group having 1-8 carbon atoms and optionally comprisesone or more catenated heteroatoms.4. The composition of any one of embodiments 1-2, wherein eachoccurrence of R_(fl) and R_(f2) is bonded together to form a ringstructure having 4-8 carbon atoms and that optionally comprises one ormore catenated heteroatoms.5. The composition of any one of embodiments 1-4, wherein theperfluorinated propenylamine has a GWP of less than 100.6. A method of making the composition of any one of embodiments 1-5, themethod comprising:

contacting a perfluorinated allylamine of general formula (2) with anactive isomerization catalyst;

carrying out a selective catalytic isomerization to form a1-propenylamine of general formula (1);

wherein the selectivity for formation of the E isomer of formula (1) isat least 70% wt. %, based on the total weight of the propenylamine inthe composition.

7. A working fluid comprising a composition according to any one ofembodiments 1-5, wherein the composition is present in the working fluidat an amount of at least 25% by weight based on the total weight of theworking fluid.8. An apparatus for heat transfer comprising:

a device; and

a mechanism for transferring heat to or from the device, the mechanismcomprising a heat transfer fluid that comprises the composition orworking fluid according to any one of embodiments 1-5 or 7.

9. An apparatus for heat transfer according to embodiment 8, wherein thedevice is selected from a microprocessor, a semiconductor wafer used tomanufacture a semiconductor device, a power control semiconductor, anelectrochemical cell, an electrical distribution switch gear, a powertransformer, a circuit board, a multi-chip module, a packaged orunpackaged semiconductor device, a fuel cell, and a laser.10. An apparatus for heat transfer according to embodiment 8, whereinthe mechanism for transferring heat is a component in a system formaintaining a temperature or temperature range of an electronic device.11. A method of transferring heat comprising:

providing a device; and

transferring heat to or from the device using a heat transfer fluid thatthe composition or working fluid according to any one of embodiments 1-5or 7.

12. The composition or working fluid of any one of embodiments 1-5 or 7,wherein at least 95 wt. % of the perfluorinated propenylamine is in theform of the E isomer, based on the total weight of the perfluorinatedpropenylamine in the composition.

The operation of the present disclosure will be further described withregard to the following detailed examples. These examples are offered tofurther illustrate various embodiments and techniques. It should beunderstood, however, that many variations and modifications may be madewhile remaining within the scope of the present disclosure.

Examples

Objects and advantages of this disclosure are further illustrated by thefollowing comparative and illustrative examples.

List of Materials: Name Description Source Antimony(V) Fluoride SbF₅Acros Organics, New Jersey Niobium(V) Fluoride NbF₅ Oakwood Chemical, W.Columbia, SC Titanium(IV) Fluoride TiF₄ Alfa-Aesar, Ward Hill, MAZirconium(IV) Fluoride ZrF₄ Alfa-Aesar, Ward Hill, MA Tantalum(V)Fluoride TaF₅ Oakwood Chemical, W. Columbia, SC Fluoroantimonic acidHSbF₆ Aldrich, Milwaukee, WI Antimony (V) SbCl₂F₃ Oakwood Chemical, W.dichlorotrifluoride Columbia, SC Antimony (V) SbCl₄F Oakwood Chemical,W. tetrachloromonofluoride Columbia, SC Triflic Acid (Anhydrous) CF₃SO₃H(> Aldrich, Milwaukee, WI 99%) Hydrogen Fluoride Pyridine-HF Aldrich,Milwaukee, WI Pyridine (70% HF) Potassium bifluoride KF-HF (99%)Aldrich, Milwaukee, WI Hydrofluoric acid HF(g) Matheson, New (Anhydrous)Brighton, MN Cesium Fluoride CsF Powder Cabot Corp., Boston, (Anhydrous)MA Potassium carbonate K₂CO₃ Aldrich, Milwaukee, WI

Comparative Example 1

Propenylamine Isomer Distribution Prepared by Decarboxylation ofPerfluorinated Acid Fluorides Over Potassium Carbonate

The perfluorinated acid fluorides listed in Table 1 were prepared byelectrochemical fluorination of the corresponding hydrocarbon esters,which were in turn prepared by Michael addition of the appropriatesecondary hydrocarbon amines to methyl methacrylate using previouslydescribed methods that are well known in the art. Thermaldecarboxylation of these perfluorinated acid fluorides over excesspotassium carbonate according to methods described in WO 2015/095285resulted in formation of a mixture of perfluorinated propenylamineisomers. Reaction conditions, total yield of propenylamine (sum of all 3isomers) and the isomer distribution as determined by GC-FID aresummarized in Table 1. GC peak assignments were confirmed by GC-MS andNMR spectroscopy. The percent of each isomer present, as determined byGC-FID area percent, is listed in Table 1, below. The results show thatthe Z-isomer of the internal olefin is consistently the major isomerformed, consistent with our finding that this is the thermodynamicallymost stable isomer.

TABLE 1 Reaction Conditions and Isomer Distribution of ComparativeExample 1 Product Isomer Distribution                   Input AcidFluoride               Rxn Temp (° C.)             Total Olefin Yield(%)

220 50 40.5 54.2 5.2

220 62 38.5 58.2 3.3

Comparative Example 2

Catalyst Screening for E/Z Isomerization of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholineand Determination of the Equilibrium E:Z Isomer Ratio

2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholinewas prepared as a 44:56 ratio of E and Z isomers and an overall purityof 98.5% by GC using the procedure described in Example 2 of WO2015/095285. Non-equilibrium mixtures of E and Z isomers were thengenerated by fractional distillation and isolation of the early and latedistillation cuts. These high purity mixtures were then used in catalystscreening experiments to determine which catalysts were active for E/Zisomerization at temperatures ranging from 20-88C. The catalyzedisomerization reactions were run neat (in the absence of solvent) undera dry nitrogen atmosphere to prevent catalyst poisoning by water. Thecatalysts and conditions used in each experiment and the starting andfinal E:Z ratios are summarized in Table 2, below.

TABLE 2 Reaction Conditions and E:Z Ratios-Comparative Example 2Catalyst Reaction Reaction Starting Final Loading Time Temp E:Z E:ZActive? Catalyst (Wt %) (Hrs) (° C.) Ratio Ratio (Y/N) SbF₅ 2.82 67.0 2020:80 22:78 Y SbF₅ 8.27 67.5 20 62:38 33:67 Y SbF₅ 5.55 24.0 88 20:8032:68 Y HSbF₆ 11.49 67.5 20 20:80 25:75 Y HSbF₆ 10.36 67.5 20 62:3832:68 Y NbF₅ 7.37 97.0 20 62:38 62:38 N TaF₅ 9.30 97.0 20 62:38 62:38 NSbCl₄F 7.31 97.0 20 62:38 62:38 N SbCl₂F₃ 8.83 97.0 20 62:38 62:38 NTiF₄ 7.67 97.0 20 62:38 62:38 N ZrF₄ 7.02 97.0 20 62:38 62:38 N CsF 6.5621.5 20 20:80 20:80 N (Anhydrous Powder) CF₃SO₃H 22.2 67.5 20 62:3862:38 N (Anhydrous) HF 4.85 67.0 20 20:80 20:80 N (Anhydrous) KF-HF 4.6967.0 20 20:80 20:80 N HF-Pyridine 12.42 67.0 20 20:80 20:80 N (70% HF)

Of the catalysts screened under these conditions, only SbF₅ and HSbF₆showed appreciable catalyst activity for E/Z isomerization. As expected,catalyst activity and rate of isomerization was greater at highertemperatures. Interestingly, in the case of the SbF₅or HSbF₆ catalysts,starting with either E-enriched or Z-enriched starting material resultedin approximately the same final E:Z ratio of 32:68, indicating that thismust be the thermodynamic equilibrium ratio of isomers for2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine.Furthermore, it was noted that the E-enriched starting mixture reachedequilibrium more quickly than the Z enriched starting mixture undersimilar reaction conditions, supporting the conclusion that the Z-isomeris the lower energy and thermodynamically preferred isomer. Thus, the Zisomer must overcome a larger activation barrier during isomerization tothe E isomer versus the reverse reaction where E isomerizes to Z.

Comparative Example 3

Determination of Thermodynamically Favored Isomer for VariousPerfluorinated 1-Propenylamines

Non-equilibrium, E-enriched mixtures of high purity perfluorinated1-propenylamines, prepared by selective catalytic isomerization of thecorresponding perfluorinated allyamines according to Example 2, werecharged under a N₂ atmosphere into a dry 25 mL, 2-necked round-bottomedflask equipped with a water-cooled condenser and N₂ inlet. In the caseof low boiling perfluorinated 1-propenylamines, such as1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine, a glassFischer-Porter bottle equipped with a stainless steel pressure head wasemployed as the reactor to allow heating above boiling point withoutevaporative losses. In each case a catalytic amount of SbF₅ was addedvia plastic pipette to the neat propenylamine mixture and the flask (orpressure vessel) was immediately sealed and the reaction mixture heatedto reaction temperature with stirring under N₂ and held at thistemperature for the period of time indicated in Table 3. At the end ofthe reaction, the reaction mixture was chilled to less than −10° C. andquenched by gradual addition of methanol followed by excess water. Afteragitating vigorously, the quenched reaction mixture was allowed to phaseseparate and the lower fluorochemical phase was isolated and filteredthrough a 0.2 micron Teflon membrane via syringe to remove insolubleparticulates. The clear filtrate was then analyzed neat by GC-FID. Thefinal E:Z isomer ratios in the isolated product, as determined by GC,are summarized in Table 3, and the starting E:Z isomer ratios areprovided for comparison. The GC assignments of E and Z isomers wereconfirmed by GC-MS and ¹⁹F NMR Spectroscopy. No significant sideproducts were detected by GC, indicating that these catalyzedisomerization reactions are very clean. The results show that all ofthese isomerization reactions proceed toward an equilibrium ratio ofisomers that favors the Z over the E isomer. Thus, this data indicatesthat for each of the Examples in Table 3, the Z isomer of the1-propenylamine is the thermodynamically more stable isomer and the Eisomer is thermodynamically less stable. Furthermore, this data suggeststhat the thermodynamic preference for the Z isomer is a generalphenomenon for 1-propenylamines of general formula (1).

TABLE 3 Reaction Conditions and E:Z Ratios - Comparative Example 3Catalyst Reaction Reaction Starting Final Loading Time Temp E:Z E:Z1-Propenylamine Catalyst (wt %) (hr) (° C.) Ratio Ratio

SbF₅ 18.51 15 70 91.3:8.7 31.1:68.9

SbF₅ 12.5  20 80 99.7:0.3 33.3:66.7

Example 1

Selective Isomerization of2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroallyl)morpholine toE-2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholineUsing Various Transition Metal Fluoride Catalysts

Samples of 2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroallyl)morpholine ofgreater than 98% purity (prepared using the procedure described inExample 2 of WO 2015/095285) were charged to a dry Pyrex round-bottomedflask equipped with a water cooled condenser and nitrogen inlet. Theperfluorinated allyl-morpholine starting material was then combined withcatalytic amounts of various anhydrous transition metal fluorides undera nitrogen atmosphere and allowed to react with magnetic stirring in theabsence of solvent at the temperature and for the period of timeindicated in Table 4. At the end of the reaction, the reaction mixturewas filtered at ambient temperature through a 0.45 micron Teflonmembrane via syringe to remove insoluble catalyst and the clear filtratewas then analyzed neat by GC-FID. The percent conversion of the terminalallyl starting material to internal olefin isomers (E&Z combined) andthe E:Z isomer ratio in the final isolated product, as determined by GC,is summarized in Table 4. The GC assignments of E and Z isomers wereconfirmed by GC-MS and ¹⁹F NMR Spectroscopy. No significant sideproducts were detected by GC, indicating that these catalyzedisomerization reactions are very clean. The results surprisinglyindicate that these isomerization catalysts are highly selective inisomerizing the perfluorinated allylmorpholine to the thermodynamicallydisfavored E-isomer of the internal olefin. In each case, very little ofthe thermodynamically favored Z isomer is formed, even at relativelyhigh temperatures, up to 85° C. Thus, this catalyzed isomerizationreaction represents a selective and cost effective method of producinghighly E-enriched2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholinein high yield and in high overall purity.

TABLE 4 Reaction Conditions and E:Z Ratios—Example 1 Catalyst ReactionReaction Loading Time Temp. % Conversion Final E:Z Catalyst (Wt %) (Hrs)(° C.) (by GC-FID) Isomer Ratio TaF₅ 12.61 88.5 20 99.60 98.1:1.9 ZrF₄8.06 18.5 85 84.09 96.6:3.4 TiF₄ 9.77 18.5 85 99.89 92.9:7.1 NbF₅ 1.193.0 85 99.99 98.3:1.7

Example 2

Selective Isomerization of Various Other Perfluorinated Allylamines toE-1-propenylamines Using NbF₅ Catalyst

High purity samples of the perfluorinated allylamines in Table 5 wereindependently charged to a dry Pyrex round-bottomed flask equipped witha water cooled condenser and nitrogen inlet. In the case of low boilingperfluorinated allylamines, such as1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-2-en-1-amine, a glassFischer-Porter bottle equipped with a stainless steel pressure head wasemployed as the reactor to allow heating above boiling point withoutevaporative losses. The perfluorinated allylamine starting material wasthen combined with a catalytic amount of anhydrous NbF₅ under a nitrogenatmosphere and allowed to react with stirring in the absence of solventat the temperature and for the period of time indicated in Table 5. Atthe end of the reaction, the reaction mixture was filtered at roomtemperature through a 0.45 micron Teflon membrane via syringe to removeinsoluble catalyst and the clear filtrate was then analyzed neat byGC-FID. The percent conversion of the terminal allyl starting materialto internal olefin isomers (E&Z combined) and the final E:Z isomer ratioin the isolated product, as determined by GC, is summarized in Table 5.The GC assignments of E and Z isomers was confirmed by GC-MS and ¹⁹F NMRSpectroscopy. No significant side products were detected by GC,indicating that these catalyzed isomerization reactions are very clean.The results indicate that all of these isomerization reactions arehighly selective in forming the thermodynamically disfavored E-isomer ofthe internal olefin. In each case, very little of the thermodynamicallyfavored Z isomer is formed. Thus, these catalyzed isomerizationreactions represent a general method of selectively producing highlyE-enriched 1-propenylamines in high yield and in high overall purity.

TABLE 5 Reaction Conditions and E:Z Ratios - Example 2 NbF₅ % CatalystReaction Reaction Conversion Final E:Z Loading Time Temp. (by GC- IsomerPerfluorinated Allylamine (Wt %) (Hrs) (° C.) FID) Ratio

4.14 3 80 99.6 99.7:0.3

5.58 3 90 99.4 97.3:2.7

3.80 3 75 99.67 91.3:8.7

Example 3

Selective Isomerization of2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholineto2,2,3,3,5,5,6,6-octafluoro-4-[(E)-1,2,3,3,3-pentafluoroprop-1-enyl]morpholineusing SbF₅ Catalyst

In a 2-neck round bottomed flask equipped with magnetic stir bar, rubberseptum, and inlet adapter connected to a dry nitrogen source, neat2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroallyl)morpholine (20g, 55.3 mmol) was slowly treated at 0° C., with SbF₅ (0.6 g, 3 mmol).The resulting solution was allowed to stir at 0° C. for 1 h, and thereaction was then quenched by addition of water (10 mL) at 0° C. Thelower fluorochemical product phase was separated and dried over Na₂SO₄.Filtration to remove the desiccating agent yielded 18 g of clear liquidproduct. Analysis by GC-FID revealed 85+% conversion of terminal allylicdouble bond to internal double bond and a final E:Z ratio of 97:3 forthe 1-propenylamine product produced. The GC assignments of E and Zisomers were confirmed by GC-MS and ¹⁹F NMR spectroscopy.

Example 4

Selective Isomerization of1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)-prop-2-en-1-amine to(E)-1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)-prop-1-en-1-amineusing SbF₅ Catalyst

In a 2-neck round bottomed flask equipped with magnetic stir bar, rubberseptum, and inlet adapter connected to a dry nitrogen source, neat1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)-prop-2-en-1-amine (25 g,88.3 mmol) was slowly treated at −50° C., with SbF₅ (1.0 g, 4.6 mmol).The resulting solution was allowed to slowly warm to 0° C. over 60 min,and was stirred at this temperature for 30 min. The reaction wassubsequently quenched by addition of water (10 mL) at 0° C. The lowerfluorochemical phase was separated and dried over Na₂SO₄. Filtration toremove the desiccating agent yielded 20 g of clear liquid product.Analysis of the product by GC-FID revealed 98+% conversion of theterminal allylic double bond to internal double bond and a final E:Zratio of 93:7 for the 1-propenylamine product produced. The GCassignments of E and Z isomers were confirmed by GC-MS and ¹⁹F NMRspectroscopy.

Example 5

Atmospheric Lifetimes and Estimated GWPs of E and Z-1-Propenylamines

The atmospheric lifetimes of 1-propenylamines were determined from theirrate of reaction with hydroxyl radicals. The pseudo-first order ratesfor the reaction of the gaseous 1-propenylamines with hydroxyl radicalwere measured in a series of experiments relative to reference compoundssuch as chloromethane and ethane. The measurements were performed in a5.7 L, heated FTIR gas cell equipped with a polished semiconductor-gradequartz window. An Oriel Instruments UV Lamp, Model 66921 equipped with a480 W mercury-xenon bulb was used to generate hydroxyl radicals byphotolyzing ozone in the presence of water vapor. The concentrations ofthe 1-propenylamine and the reference compound were measured as afunction of reaction time using an I-Series FTIR from Midac Corporation.The atmospheric lifetimes were calculated from the reaction rates forthe 1-propenylamines relative to the reference compounds and thereported lifetime of the reference compounds as shown below:

$\tau_{x} = {\tau_{r} \cdot \frac{k_{r}}{k_{x}}}$

where τ_(x) is the atmospheric lifetime of the 1-propenylamine, τ_(r) isthe atmospheric lifetime of the reference compound, and k_(x) and k_(r)are the rate constants for the reaction of hydroxyl radical with theisomeric 1-propenylamines and the reference compound, respectively.

Global warming potentials (GWPs) have been estimated for the1-propenylamine isomers using these atmospheric lifetimes. The GWPs werecalculated according to the Intergovernmental Panel on Climate Change(IPCC) 2013 method using a 100 year integration time horizon (ITH). Theradiative efficiencies used in these calculations were based upon theinfrared cross-sections measured on the mixture of E and Z isomers foreach 1-propenylamine. Results for the E and Z isomers of1-propenylamines are shown in Table 6.

TABLE 6 Measured Atmospheric Lifetimes and Estimated GWPs of E andZ-1-Propenylamines Atmospheric Estimated GWP Lifetime (Yrs) (100-yr ITH)1-Propenylamine E-isomer Z-isomer E-isomer Z-isomer (CF₃)₂N—CF═CFCF₃0.71 1.9  50 140 C₂F₅(CF₃)N—CF═CFCF₃ 1.4  3.5 110 270

0.80 2.6  80 250

Example 6

Isomerization of2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholineto(E)-2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholinewith AlCl₃

In a 25-mL two-neck round bottom flask equipped with magnetic stir bar,thermocouple, and inlet adapter connected via tubing to a Schlenk line,2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine(10 g, 27.7 mmol) was introduced under a stream of dry nitrogen followedby AlCl₃ (5 mol %, 0.18 g, 1.4 mmol). The resulting suspension wasstirred at room temperature for 16 h or at 80° C. for 2 h. The reactionwas subsequently quenched by addition of water (10 mL) at 4° C. Thelower fluorochemical phase was separated and dried over Na₂SO₄.Filtration to remove the desiccating agent yielded 9.3 g of clear liquidproduct. Analysis of the product by GC-FID revealed 99.9% conversion ofthe terminal allylic double bond to internal double bond and a final E:Zratio of 97:3 for the 1-propenylamine product produced. The GCassignments of E and Z isomers were confirmed by GC-MS and ¹⁹F NMRspectroscopy.

Example 7

Isomerization of1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-2-en-1-amine to(E)-1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine withAlC13

In a 25-mL two-neck round bottom flask equipped with magnetic stir bar,rubber septum, and inlet adapter connected via tubing to a Schlenk line,1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-2-en-1-amine (10 g,35.3 mmol) was introduced under a stream of dry nitrogen followed byAlCl₃ (5 mol %, 0.23 g, 1.76 mmol). The resulting suspension was stirredat room temperature for 16 h. For high temperature isomerization (i.e.;80° C.), the substrate and catalyst were placed in a glass pressurevessel and heated for 2 h. The reaction was subsequently quenched byaddition of water (10 mL) at 4° C. The lower fluorochemical phase wasseparated and dried over Na₂SO₄. Filtration to remove the desiccatingagent yielded 9.1 g of clear liquid product. Analysis of the product byGC-FID revealed 99.9% conversion of the terminal allylic double bond tointernal double bond and a final E:Z ratio of 97:3 for the1-propenylamine product produced. The GC assignments of E and Z isomerswere confirmed by GC-MS and ¹⁹F NMR spectroscopy.

Example 8

Isomerization of2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholineto(E)-2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholinewith SbCl₅

In a 25-mL two-neck round bottom flask equipped with magnetic stir bar,thermocouple, and inlet adapter connected via tubing to a Schlenk line,2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine(10 g, 27.7 mmol) was introduced under a stream of dry nitrogen followedby SbC15 (5 mol %, 0.42 g, 1.4 mmol). The resulting solution was stirredat room temperature for 24 h or at 80° C. for 2 h. The reaction wassubsequently quenched by addition of water (10 mL) at 4° C. The lowerfluorochemical phase was separated and dried over Na₂SO₄. Filtration toremove the desiccating agent yielded 9.5 g of clear liquid product.Analysis of the product by GC-FID revealed 90% and 99.9% conversion at25° C. and 80° C., respectively, of the terminal allylic double bond tointernal double bond and a final E:Z ratio of 97:3 for the1-propenylamine product produced in both cases. The GC assignments of Eand Z isomers were confirmed by GC-MS and ¹⁹F NMR spectroscopy.

Example 9

Isomerization of1,1,2,3,3-pentafluoro-N,N-bis(perfluoropropyl)prop-2-en-1-amine to(E)-1,2,3,3,3-pentafluoro-N,N-bis(perfluoropropyl)prop-1-en-1-amine withAlCl₃

To an 8 mL vial equipped with a stir bar was charged AlC13 (28 mg, 21mmol, 5.0 mol %) and1,1,2,3,3-pentafluoro-N,N-bis(perfluoropropyl)prop-2-en-1-amine (2.0 g,4.1 mmol). The resultant mixture was allowed to stir at room temperaturefor 16 h before filtering through a 0.45 μm PVDF syringe filter to givea colorless liquid filtrate (1.95 g). GC analysis of the filtrateconfirmed 99% conversion of the starting material and anE:Z-1-aminopropene ratio of 98:2. GC analysis also revealed that atleast 96.5% of the filtrate comprised the expected isomerizationproducts, E- and Z-1-aminopropene. All structures were confirmed byGC-MS analysis and ¹⁹F NMR spectroscopy.

Various modifications and alterations to this disclosure will becomeapparent to those skilled in the art without departing from the scopeand spirit of this disclosure. It should be understood that thisdisclosure is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only with the scope of thedisclosure intended to be limited only by the claims set forth herein asfollows. All references cited in this disclosure are herein incorporatedby reference in their entirety.

What is claimed is:
 1. A method of making the composition of claim 1,the method comprising: contacting a perfluorinated allylamine of generalformula (2) with an active isomerization catalyst;

carrying out a selective catalytic isomerization to form a1-propenylamine of general formula (1);

wherein the selectivity for formation of the E isomer of formula (1) isat least 60% wt. %, based on the total weight of the propenylamine inthe composition.
 2. A working fluid comprising a composition accordingto claim 1, wherein the composition is present in the working fluid atan amount of at least 25% by weight based on the total weight of theworking fluid.
 3. An apparatus for heat transfer comprising: a device;and a mechanism for transferring heat to or from the device, themechanism comprising a heat transfer fluid that comprises thecomposition or working fluid according to claim
 1. 4. An apparatus forheat transfer according to claim 3, wherein the device is selected froma microprocessor, a semiconductor wafer used to manufacture asemiconductor device, a power control semiconductor, an electrochemicalcell, an electrical distribution switch gear, a power transformer, acircuit board, a multi-chip module, a packaged or unpackagedsemiconductor device, a fuel cell, and a laser.
 5. An apparatus for heattransfer according to claim 3, wherein the mechanism for transferringheat is a component in a system for maintaining a temperature ortemperature range of an electronic device.
 6. A method of transferringheat comprising: providing a device; and transferring heat to or fromthe device using a heat transfer fluid that the composition or workingfluid according to claim 1.